EP0316696A2 - Organopolysiloxane elastomers having improved electrical properties and insulators coated therewith - Google Patents
Organopolysiloxane elastomers having improved electrical properties and insulators coated therewith Download PDFInfo
- Publication number
- EP0316696A2 EP0316696A2 EP88118492A EP88118492A EP0316696A2 EP 0316696 A2 EP0316696 A2 EP 0316696A2 EP 88118492 A EP88118492 A EP 88118492A EP 88118492 A EP88118492 A EP 88118492A EP 0316696 A2 EP0316696 A2 EP 0316696A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- organopolysiloxane
- aluminum trihydrate
- radicals
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 37
- 239000012212 insulator Substances 0.000 title claims description 25
- 229920001971 elastomer Polymers 0.000 title claims description 10
- 239000000806 elastomer Substances 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 57
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 22
- 239000000615 nonconductor Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- HDNXAGOHLKHJOA-UHFFFAOYSA-N n-[bis(cyclohexylamino)-methylsilyl]cyclohexanamine Chemical group C1CCCCC1N[Si](NC1CCCCC1)(C)NC1CCCCC1 HDNXAGOHLKHJOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 150000001412 amines Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- -1 polydimethylsiloxane Polymers 0.000 description 88
- 150000003254 radicals Chemical group 0.000 description 13
- 239000000945 filler Substances 0.000 description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000005840 aryl radicals Chemical class 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIBXVTMWHMMKGV-UHFFFAOYSA-N 2-trimethylsilylethanamine Chemical compound C[Si](C)(C)CCN NIBXVTMWHMMKGV-UHFFFAOYSA-N 0.000 description 1
- YAIQGOCTSOUDDP-UHFFFAOYSA-N 3,3,5-trimethyl-n-[phenyl-bis[(3,3,5-trimethylcyclohexyl)amino]silyl]cyclohexan-1-amine Chemical compound C1C(C)(C)CC(C)CC1N[Si](C=1C=CC=CC=1)(NC1CC(C)(C)CC(C)C1)NC1CC(C)(C)CC(C)C1 YAIQGOCTSOUDDP-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VWESNXXALVPVSS-UHFFFAOYSA-N 4-dimethylsilyl-N-ethenylbutan-1-amine Chemical compound C(=C)NCCCC[SiH](C)C VWESNXXALVPVSS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- UZMMLKBXLUHGCG-UHFFFAOYSA-N N-(3-dimethylsilylpropyl)aniline Chemical compound C1(=CC=CC=C1)NCCC[SiH](C)C UZMMLKBXLUHGCG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910020485 SiO4/2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- HIMXYMYMHUAZLW-UHFFFAOYSA-N [[[dimethyl(phenyl)silyl]amino]-dimethylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C)(C)N[Si](C)(C)C1=CC=CC=C1 HIMXYMYMHUAZLW-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical class CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- VQPKAMAVKYTPLB-UHFFFAOYSA-N lead;octanoic acid Chemical compound [Pb].CCCCCCCC(O)=O VQPKAMAVKYTPLB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PLUXWTRVVOADTC-UHFFFAOYSA-N n-[(cyclohexylamino)-dimethylsilyl]cyclohexanamine Chemical compound C1CCCCC1N[Si](C)(C)NC1CCCCC1 PLUXWTRVVOADTC-UHFFFAOYSA-N 0.000 description 1
- OGVVDLMGEQARAV-UHFFFAOYSA-N n-[bis(butan-2-ylamino)-methylsilyl]butan-2-amine Chemical compound CCC(C)N[Si](C)(NC(C)CC)NC(C)CC OGVVDLMGEQARAV-UHFFFAOYSA-N 0.000 description 1
- KVCBAJMIFZNEFZ-UHFFFAOYSA-N n-[bis(butylamino)-hexylsilyl]butan-1-amine Chemical compound CCCCCC[Si](NCCCC)(NCCCC)NCCCC KVCBAJMIFZNEFZ-UHFFFAOYSA-N 0.000 description 1
- VJDVRUZAQRISHN-UHFFFAOYSA-N n-[bis(dimethylamino)-phenylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](N(C)C)(N(C)C)C1=CC=CC=C1 VJDVRUZAQRISHN-UHFFFAOYSA-N 0.000 description 1
- WBRWEYCGDXVTSR-UHFFFAOYSA-N n-[bis(ethylamino)-methylsilyl]ethanamine Chemical compound CCN[Si](C)(NCC)NCC WBRWEYCGDXVTSR-UHFFFAOYSA-N 0.000 description 1
- ZZOCQIFWXMQPQA-UHFFFAOYSA-N n-[bis(heptylamino)-methylsilyl]heptan-1-amine Chemical compound CCCCCCCN[Si](C)(NCCCCCCC)NCCCCCCC ZZOCQIFWXMQPQA-UHFFFAOYSA-N 0.000 description 1
- GQFQFJSBIAYIFR-UHFFFAOYSA-N n-[dianilino(ethenyl)silyl]aniline Chemical compound C=1C=CC=CC=1N[Si](NC=1C=CC=CC=1)(C=C)NC1=CC=CC=C1 GQFQFJSBIAYIFR-UHFFFAOYSA-N 0.000 description 1
- PKOGAUCTWHHRCG-UHFFFAOYSA-N n-[dianilino(methyl)silyl]aniline Chemical compound C=1C=CC=CC=1N[Si](NC=1C=CC=CC=1)(C)NC1=CC=CC=C1 PKOGAUCTWHHRCG-UHFFFAOYSA-N 0.000 description 1
- XFPHAUYBBDTGMF-UHFFFAOYSA-N n-[dimethyl(phenyl)silyl]oxy-n-ethylethanamine Chemical compound CCN(CC)O[Si](C)(C)C1=CC=CC=C1 XFPHAUYBBDTGMF-UHFFFAOYSA-N 0.000 description 1
- PNYNUPZUHYVNDH-UHFFFAOYSA-N n-[ethenyl-bis(propylamino)silyl]propan-1-amine Chemical compound CCCN[Si](NCCC)(NCCC)C=C PNYNUPZUHYVNDH-UHFFFAOYSA-N 0.000 description 1
- IQQUUVWEFNMZSD-UHFFFAOYSA-N n-[ethyl-bis[hexyl(methyl)amino]silyl]-n-methylhexan-1-amine Chemical compound CCCCCCN(C)[Si](CC)(N(C)CCCCCC)N(C)CCCCCC IQQUUVWEFNMZSD-UHFFFAOYSA-N 0.000 description 1
- QMOVJRNIFJIGLR-UHFFFAOYSA-N n-[tris(butylamino)silyl]butan-1-amine Chemical compound CCCCN[Si](NCCCC)(NCCCC)NCCCC QMOVJRNIFJIGLR-UHFFFAOYSA-N 0.000 description 1
- GBJMFCGAYQHVHF-UHFFFAOYSA-N n-ethyl-n-trimethylsilyloxyethanamine Chemical compound CCN(CC)O[Si](C)(C)C GBJMFCGAYQHVHF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YSPHIXJPYVFLLJ-UHFFFAOYSA-N n-trimethylsilylpropan-2-amine Chemical compound CC(C)N[Si](C)(C)C YSPHIXJPYVFLLJ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000005386 organosiloxy group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Definitions
- the present invention relates to organopolysiloxane elastomers having improved electrical properties and more particularly to organopolysiloxane compositions which may be applied to electrical insulators to provide improved arc resistance.
- compositions have been described heretofore having improved electrical properties.
- U. S. Patent No. 3,965,065 to Elliott describes a method for preparing a composition having improved electrical properties which comprises heating a mixture containing aluminum hydrate and an organopolysiloxane which is convertible to an elastomeric solid to a temperature above 100°C for at least thirty (30) minutes.
- Niemi describes a method for preparing improved high voltage insulators in U. S. Patent No. 4,476,155 in which a composition containing the product obtained by mixing a hydroxyl endblocked polydimethylsiloxane with aluminum hydroxide and a ketoxime functional silane, is applied to the outer surface of an insulator.
- Penneck discloses high voltage insulating materials in U. S. Patent No. 4,001,128 in which the insulating materials contain organic synthetic polymeric materials and an anti-tracking filler system containing at least 20 percent by weight of alumina trihydrate and at least one percent by weight based on the weight of the polymer and filler system of a chemically treated silica filler.
- Penneck discloses tracking resistant insulating materials in U. S. Patent No. 4,189,392, in which the insulating materials contain a polymeric material and an anti-tracking filler and a fluorine substituted compound which is a hydrophobic, non-ionic compound having a fluorine-substituted aliphatic carbon chain linked to a group having an affinity for the polymeric material and/or the anti-tracking filler.
- composition comprising an organopolysiloxane containing reactive groups, an amine crosslinking agent which is capable of crosslinking with the organopolysiloxane and aluminum trihydrate, which has been treated to impart hydrophobic properties thereto.
- the resultant composition may be applied to the outer surface of electrical insulators and crosslinked in the presence of atmospheric moisture.
- organopolysiloxanes employed herein are preferably diorganopolysiloxanes having terminal reactive groups and more preferably organopolysiloxanes having terminal hydroxyl groups. These organopolysiloxanes are well known and have been employed heretofore in room temperature vulcanizable (RTV) compositions.
- the preferred diorganopolysiloxanes which have terminal hydroxyl groups, may be represented by the formula where each R is a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, x has an average value of from 0.99 to 1.01, y has an average value of from 1.99 to 2.01, x + y is equal to 3, n is a number of at least 3 and preferably at least 50.
- hydroxyl groups linked to the silicon atoms of the organopolysiloxane can be replaced in part or entirely by other reactive groups such as hydrogen atoms, halogen atoms, alkoxy groups, aryloxy radicals and radicals of the formula R′NH-, where R′ is a cycloalkyl radical of from 5 to 12 carbon atoms.
- siloxane polymers are essentially linear, hence they are predominately, i.e., at least 90 mole percent are R2SiO units.
- siloxane units, other than the disiloxane (R2SiO) units may be present in an amount up to about 5 mol percent and more preferably below about 2 mol percent.
- siloxane units such as RSiO 3/2 units, R3SiO 1 ⁇ 2 units and/or SiO 4/2 units, where R is the same as above can be present mostly as impurities.
- each R can be a monovalent hydrocarbon radical of up to 18 carbon atoms.
- radicals represented by R include alkyl radicals such as the methyl, ethyl, n-propyl, isopropyl, dodecyl and octadecyl radicals; alkenyl radicals such as vinyl, allyl, hexenyl and octadecenyl radicals; cycloalkyl radicals such as the cyclobutyl, cyclopentyl, cyclohexyl and cyclodecyl radicals; cycloalkenyl radicals such as the cyclobutenyl, cyclopentenyl, cyclohexenyl and cyclodecenyl radicals; aryl radicals such as phenyl, xenyl, naphthyl and the phenanthryl radicals; aralkyl radicals such as the benzyl, B
- Substituted hydrocarbon radicals represented by R include halogen hydrocarbon radicals such as o-, m- and p-chlorophenyl and bromophenyl radicals, ⁇ , ⁇ , ⁇ -trifluorotolyl, 3,3,3-trifluoropropyl, chloro-, fluoro- and bromoderivatives of the various hydrocarbon radicals set forth above as well as cyanoalkyl radicals such as B-cyanoethyl, cyanopropyl, cyano-n-butyl, cyano-n-propyl and omega-cyanooctadecyl radicals.
- halogen hydrocarbon radicals such as o-, m- and p-chlorophenyl and bromophenyl radicals, ⁇ , ⁇ , ⁇ -trifluorotolyl, 3,3,3-trifluoropropyl, chloro-, fluoro- and bromoderivatives
- the radicals represented by R have less than 8 carbon atoms and more preferably R represents methyl, ethyl, propyl, vinyl, phenyl, and 3,3,3-trifluoropropyl radicals.
- R radicals on a single silicon atom can be the same or different and various units in the siloxane chain can be the same or different homopolymers, e.g., dimethylsiloxane units, copolymers of, for example, dimethylsiloxane and methylvinylsiloxane units, or phenylmethylsiloxane units and mixtures thereof.
- the siloxane polymers employed can vary from relatively mobile fluids (viscosity 50 mPa.s at 25°C) to gum-like materials having viscosities in the range of 106 mPa.s at 25°C. This can be seen from the value of n in the general formula above, where n is at least 3 and is preferably at least 50, but can have a value as high as 2,000,000.
- the preferred siloxane polymers are those having viscosities in the range of from 200 to 200,000 mPa.s at 25°C.
- siloxanes are known and have been described in, for example, U. S. Patents Nos. 3,294,732; 3,127,363; 3,105,061 and others.
- the room temperature vulcanizable organopolysiloxane compositions are prepared by mixing under anhydrous conditions organopolysiloxanes containing reactive groups, preferably hydroxyl groups, with an amine-substituted silicon compound capable of reacting with the organopolysiloxane reactive groups and having an average of at least two -NR1 ⁇ 2 groups bonded to a silicon atom per molecule, where R1 is a monovalent hydrocarbon radical which preferably has up to 18 carbon atoms or hydrogen, and more preferably at least one R1 is hydrogen.
- Amine-substituted silicon compounds which may be employed as crosslinking agents are aminosilanes of the formula R2 4-z Si(NR1 ⁇ 2 ) z where R1 is the same as above and R2 is a monovalent radical, preferably a monovalent hydrocarbon radical, having from 1 to 18 carbon atoms, and z has an average value of at least 2 and more preferably from 2 to 4 per molecule and partial hydrolyzates thereof.
- the aminosilanes which are employed as crosslinking agents preferably may contain an average of 3 or 4 amino substituents per silicon atom and 0 or 1 alkyl, or aryl, or alkaryl or aralkyl radicals per silicon atom.
- the trifunctional aminosilanes may be represented by the formula R2Si(NR1 ⁇ 2 )3 and the tetra-functional silanes by the formula Si(NR1 ⁇ 2 )4, where R1 and R2 are the same as above.
- monovalent hydrocarbon radicals represented by R1 are alkyl radicals, such as the methyl, ethyl, propyl or octadecyl radicals, aryl radicals, such as the phenyl or anthracyl or a cycloalkyl radical such as the cyclohexyl radical or an aralkyl radical such as the benzyl or phenylethyl radical or an alkaryl radical such as the tolyl or xylyl radicals.
- monovalent hydrocarbon radicals represented by R2 are an alkyl, aryl, cycloalkyl, alkaryl or aralkyl radicals.
- R1 radicals also apply to the R2 radicals, when R1 is a monovalent hydrocarbon radical. Only one type of aminosilane need be employed; however, mixtures of aminosilanes may also be employed as crosslinking agents.
- aminosiloxanes having the general formulas and aminosilylalkanes having the general formula where R, R1 and R2 are the same as above, R3 is a saturated or unsaturated divalent hydrocarbon radical having up to 10 carbon atoms, m is a number of from 0 to 50, v is a number of from 0 to 3, w is a number of from 0 to 3 and the sum of v + w is equal to at least 3.
- Divalent saturated hydrocarbon radicals represented by R3 above are methylene, ethylene, propylene, butylene, hexylene, octylene and decylene radicals.
- Divalent unsaturated hydrocarbon radicals represented by R3 are ethenylene, propenylene, butenylene, hexenylene, octenylene and decenylene radicals.
- An example of a divalent cyclic hydrocarbon radical is the phenylene radical.
- aminosilanes and aminosiloxanes and aminosilylalkanes employed as crosslinking agents are described, for example, in U. S. Patents Nos. 3,408,325 to Hittmair et al; 3,464,951 to Hittmair et al; 3,452,964 to Creamer; 3,644,434 to Hittmair et al; and 3,816,164 to Pepe et al, all of which are incorporated herein by reference.
- R 2 4 -z Si[NHCH(R4)2] z R2 and z are the same as above
- R4 which may be the same or different represent monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms, and more preferably from 1 to 4 carbon atoms.
- R4 is an alkyl radical, such as the methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl and octadecyl radicals.
- radicals represented by R4 are aryl radicals such as the phenyl radical, alkaryl radicals such as the tolyl and ethylphenyl radicals and aralkyl radicals such as the benzyl and the B-phenylethyl radicals.
- crosslinking agents represented by the above formula are silanes of the formula CH3Si[NHCH(CH3)C2H5]3 and silazanes of the general formula where R1, R2 are the same as above and g is 0 or a number having a value of at least 1 and preferably less than about 100.
- silicon compounds which can be used as crosslinking agents are aminosiloxanes of the formula R 2 3 SiO(SiR2O) m Si[NHCH(R4)2]3 where R, R2, R4 and m are the same as above.
- crosslinking agents may be prepared, for example, by reacting halosilanes with a sec-butylamine.
- These secondary butylamine crosslinking agents and their method of preparation are described in U. S. Patent No. 3,923,736 to Nitzsche et al, which is incorporated herein by reference.
- the silicon valences of the amine substituted silicon compounds which are not satisfied by the -NCH(R4)2 groups are preferably satisfied by monovalent hydrocarbon radicals, cyanoalkyl radicals, Si-bonded hydroxyl groups and/or siloxane oxygen atoms.
- the amine-substituted organosilicon compounds are employed in amounts which will provide at least one gram equivalent silicon atom of the amih, substituted organosilicon compound per gram equivalent of reactive groups on the organopolysiloxane. Generally from about 0.2 to 40 parts by weight of amine substituted organosilicon compound is added for each 100 parts by weight of the organopolysiloxane containing reactive groups.
- the composition also contains aluminum trihydrate, which has been treated to impart hydrophobic properties thereto.
- the aluminum trihydrate has a specific surface area in the range of from about 1 to 20 m2/g and more preferably from about 2 to 15 m2/g.
- the average particle size ranges from about 2 to 10 ⁇ m and more preferably from about 2 to 5 ⁇ m.
- about 97 percent of the aluminum trihydrate has a particle size of less than about 10 ⁇ m.
- the aluminum trihydrate is present in an amount of from about 40 to 75 percent by weight and more preferably from about 50 to 70 percent by weight based on the weight of the organopolysiloxane polymer and the aluminum trihydrate.
- Organosilicon compounds capable of imparting hydrophobic properties to inorganic substances may be used to treat the aluminum trihydrate of this invention.
- Organosilicon compounds which may be employed to treat the aluminum trihydrate are those having the general formula (R3Si) a Z or R a ,SiZ′ 4-a′ wherein R which may be the same or different represents monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals having up to 18 carbon atoms, Z and Z′ represent halogen, hydrogen or a radical of the formula -OH, -OR4, NX2, -NR4X, -ONR4, or -OOCR4 and when a is 2, then Z may also represent -O- or -NX-; R4 is a monovalent hydrocarbon radical having up to 18 carbon atoms and more preferably R4 is an alkyl radical having from 1 to 4 carbon atoms; X is hydrogen or has the same meaning as R4, a is 1 or 2 and a′ is 1, 2 or 3.
- organosilicon compounds which may be employed are octamethycyclotetrasiloxane and/or dimethylpolysiloxanes having from 2 to 12 siloxane units per molecule in which the dimethylpolysiloxanes have an Si-bonded hydroxyl group in each of their terminal units.
- the monovalent and halogenated monovalent hydrocarbon radicals represented by R in the organosilicon compounds may be the same as the R radicals linked to the diorganopolysiloxanes.
- Suitable monovalent hydrocarbon radicals having from 1 to 18 carbon atoms are alkyl radicals, cycloalkyl radicals, alkenyl radicals, aryl radicals, alkaryl radicals, aralkyl radicals and halogenated derivatives thereof.
- halogen atoms represented by Z and Z′ are chlorine, bromine and iodine, with chlorine being the preferred example, since it is readily available.
- hydrocarbon radicals represented by R4 are the methyl, ethyl, propyl and butyl radicals. Additional examples of hydrocarbon radicals represented by R4 are described in the following examples of organosilicon compounds which impart hydrophobic properties to aluminum trihydrate.
- organosilicon compounds which may be employed to impart hydrophobic properties to aluminum trihydrate are hexamethyldisilazane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylethoxysilane, trimethylaminosilane, trimethylchlorosilane, dimethyldiethoxysilane, trimethylsilylisopropylamine, trimethylsilylethylamine, phenyldimethylsilylpropylamine, vinyldimethylsilylbutylamine, diethylaminoxytrimethylsilane, diethylaminoxyphenyldimethylsilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisilazane, dimethyldichlorosilane, dimethyldimethoxysilane, diphenyldiethoxysilane, vinylmethyldimethoxy
- the organosilicon compound used to treat the aluminum trihydrate be a vinyltrialkoxysilane having 1 to 2 carbon atoms per alkoxy group because they do not release any by-products which may have a detrimental effect on the dispersions of this invention.
- Mixtures of various organosilicon compounds may also be employed in the treatment of aluminum trihydrate to impart hydrophobic properties thereto.
- the amount of organosilicon compounds used in the surface treatment of the aluminum trihydrate be from about 0.1 to 10 percent by weight based on the weight of the aluminum trihydrate.
- the aluminum trihydrate can be reacted with the organosilicon compounds by any conventional technique known in the art for reacting inorganic substances which are solid at room temperature.
- the aluminum trihydrate can react with hydrophobic imparting organosilicon compounds which evaporate at room temperature at 760mm Hg (abs.), in a sealed container, such as, for example, a polyethylene bag, for a period of time under ambient conditions.
- the aluminum trihydrate can be mixed in a mechanical mixing device with a liquid hydrophobic imparting organosilicon compound or in a fluidized bed, and if desired, in the presence of a stream of inert gas.
- the reaction of the aluminum trihydrate with the organosilicon compound can be accelerated by using catalysts such as ammcnia or amines at the rate of from about 0.3 to 3 percent by weight based on the weight of the aluminum trihydrate.
- compositions of this invention may be prepared by mixing the various ingredients in any order desired; however, the mixture should be prepared in an atmosphere which is substantially free of water.
- compositions of this invention may also contain additives such as compression-set additives, pigments, soluble dyes, aromatics (essential oils), oxidation inhibitors, heat stabilizers, flame retardants and light stabilizers, plasticizers and softeners such as trimethylsiloxy endblocked dimethylpolysiloxane fluids, reinforcing fillers and non-reinforcing fillers.
- additives such as compression-set additives, pigments, soluble dyes, aromatics (essential oils), oxidation inhibitors, heat stabilizers, flame retardants and light stabilizers, plasticizers and softeners such as trimethylsiloxy endblocked dimethylpolysiloxane fluids, reinforcing fillers and non-reinforcing fillers.
- reinforcing fillers and non-reinforcing fillers are quartz, diatomaceous earth, calcium silicate, zirconium silicate, so-called "molecular sieves", metal oxide powders, such as titania, alumina, iron oxide, zinc oxide and calcium carbonate.
- Fibrous fillers for example, asbestos, glass fibers or organic fibers can also be used.
- the fillers can advantageously be treated by known methods to include organosiloxy or alkoxy groups on their surface. Mixtures of different fillers may be added to the compositions of this invention.
- the amount of filler may vary over a broad range, preferably from 0 to 90 percent by weight, based on the total weight of the organopolysiloxane and filler; however, the amount of filler should not be so great as to degrade the arc resistance or current leakage supression of the elastomeric coating.
- condensation catalysts such as those disclosed in, for example, U. S. Patents Nos. 2,843,555; 2,127,363; and 3,082,527.
- suitable condensation catalysts are metallic salts and organometallic salts of carboxylic acids, such as lead octoate, dibutyltin dilaurate and dibutyltin salts of aliphatic carboxylic acids which are branched in the alpha-position to the carboxyl groups and have from 9 to 11 carbon atoms, amines, such as 3-ethoxypropylamine-1, and silanes which have at least one amine group bonded via carbon to silicon and at least one monovalent hydrocarbon radical or a hydrocarbon radical substituted by an amine group and/or alkoxy group, and bonded via oxygen to silicon in each molecule.
- Silanes of the latter which not only act as condensation catalysts but as adhesion promoters for improving the adhesion of the elastomers to the substrates, are N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane or a compound of the formula CH3Si[O(CH2)2NH2]2(CH2)3O(CH2)2NH2 .
- condensation catalysts are generally employed in amounts of from 0.01 to 5 percent by weight and more preferably from about 0.05 to 1 percent by weight, based on the total weight of the composition.
- the amount may range from about 0.2 to about 2 percent by weight, based on the weight of the organopolysiloxane and aluminum trihydrate.
- compositions of this invention are preferably prepared by mixing the treated aluminum trihydrate with the organopolysiloxane containing reactive groups and the mixture deaired.
- the amine-substituted organosilicon crosslinking agent and catalyst, if used, is then added to the mixture under anhydrous conditions.
- compositions of this invention may be stored for long periods of time under anhydrous conditions without deletrious effects and then crosslinked by merely exposing them to atmospheric moisture at room temperature.
- compositions of the present invention are especially useful for coating high voltage apparatus where it is essential that a component be insulated from the sur rounding elements.
- High voltage insulators preferably ceramic or plastic insulators
- the compositions of this invention may be coated with the compositions of this invention by conventional methods, such as spraying, dipping or brushing.
- the compositions are dispersed in a non-reactive solvent for ease of application.
- non-reactive solvents which may be employed are hydrocarbon solvents such as toluene, xylene, naphtha and chlorinated hydrocarbon solvents such as chlorothene.
- Preferred solvent are chlorinated hydrocarbon solvents, especially chlorothene and V.M.&P naphtha.
- the amount of non-reactive solvent is not critical and may range up to about 80 percent by weight, based on the weight of the composition.
- the coatings of this invention may be crosslinked by exposing the coating to atmospheric moisture. Crosslinking may be accelerated by applying heat or by adding water in addition to that contained in the atmosphere or by the addition of carbon dioxide.
- the coating preferably ranges from about 0.2 to about 2 mm in thickness.
- a coating thickness above about 2 mm may be applied to the insulators, if desired. It has been found that a thicker coating may be more resistant to arcing than thinner coatings, such as those having a thickness of less than about 0.2 mm.
- An advantage of the present invention is that a coated insulator can be manufactured in place.
- Insulators such as ceramic suspension insulators, strings, ceramic post insulators, composite suspension insulators, filled-resin post insulators and cable terminations can be coated in the field by applying the compositions of this invention on the surfaces of the insulators and thereafter exposing the coated surface to atmospheric moisture to crosslink the same.
- the resultant coating forms a hydrophobic arc-resistant surface.
- insulators may be sprayed on line and the line re-energerized while the coating dries and cures in the presence of atmospheric moisture.
- compositions are useful in a number of applications where it is necessary to resist erosion and/or control current leakage, and are especially useful in electrical components exposed to voltages above 1 kV.
- the compositions may be used in electrical power transmission and distribution systems, as for example, insulator materials for high voltage components, as insulators for cable terminations, fuse covers, transformer covered and as insulation coatings.
- the resultant dispersion is molded to form test specimens and exposed to atmospheric moisture for 7 days.
- the skin-over time is 6 minutes and the tack-free time is 11 minutes.
- the physical properties are determined after curing for 7 days in atmospheric moisture. Physical Properties Durometer, Shore A 55 Tensile strength 2,069 MPa (300 psi) Elongation percent 125 Tear strength 5260 N/m ( 30 ppi)
- the arc resistance of a cured sample is determined in accordance with ASTMD-495-73.
- the contact angle is measured by the sessile drop technique in which drops of water about 2 mm in diameter are applied from a syringe to the surface of the sample after it has cured for 7 days.
- the contact angle is measured about 30 seconds after applying the water using a telescope fitted with a goniometer eyepiece.
- Contact angle of the cured sample is 103°.
- Example 1 The procedure of Example 1 is repeated, except that 150 parts of an untreated aluminum trihydrate (available from Solem Industries, Inc. as SB-632) is substituted for the treated aluminum trihydrate.
- the resultant mixture is formed into test specimens and exposed to atmospheric moisture.
- the skin-over time is 11 minutes and the tack-free time is 18 minutes.
- the physical properties are determined. Physical Properties Durometer, Shore A 50 Tensile strength 1,655 MPa (240 psi) Elongation, percent 150 Tear strength 5260 N/m ( 30 ppi)
- the contact angle which is measured in accordance with the procedure described in Example 1, is 90°.
- Example 1 The procedure of Example 1 is repeated, except that 67 parts of treated aluminum trihydrate is substituted for 150 parts of treated aluminum trihydrate.
- the resultant composition exhibited good arc resistance.
- Example 1 The procedure of Example 1 is repeated, except that 300 parts of treated aluminum trihydrate is substituted for 150 parts of treated aluminum trihydrate.
- the arc resistance of the resultant composition before failure is greater than 420 seconds.
- the solvent dispersion prepared in accordance with the procedure of Example 1 is applied to the surface of a ceramic insulator as a uniform coating about 1 mm in thickness and cured by exposure to atmospheric moisture.
- the resultant coating provides a hydrophobic and arc resistant surface which shows excellent adhesion to the insulator surface.
- Example 2 The procedure of Example 1 is repeated, except that 10 parts of each of the following crosslinking agents are substituted for 10 parts of methyltris(cyclohexylamino)silane in the above composition: Methyltris(ethylamino)silane, methyltris(phenylamino)silane, methyltris(n-heptylamino)silane, phenyltris(3,5,5-trimethylcyclohexylamino)silane, methyltris(sec-butylamino)silane, tetrakis(n-butylamino)silane, phenyltris(dimethylamino)silane, hexyltris(n-butylamino)silane, ethyltris(methylhexylamino)silane, vinyltris(phenylamino)silane and a mixture containing 30 percent by
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Abstract
Description
- The present invention relates to organopolysiloxane elastomers having improved electrical properties and more particularly to organopolysiloxane compositions which may be applied to electrical insulators to provide improved arc resistance.
- Various compositions have been described heretofore having improved electrical properties. For example, U. S. Patent No. 3,965,065 to Elliott describes a method for preparing a composition having improved electrical properties which comprises heating a mixture containing aluminum hydrate and an organopolysiloxane which is convertible to an elastomeric solid to a temperature above 100°C for at least thirty (30) minutes.
- Niemi describes a method for preparing improved high voltage insulators in U. S. Patent No. 4,476,155 in which a composition containing the product obtained by mixing a hydroxyl endblocked polydimethylsiloxane with aluminum hydroxide and a ketoxime functional silane, is applied to the outer surface of an insulator.
- Penneck discloses high voltage insulating materials in U. S. Patent No. 4,001,128 in which the insulating materials contain organic synthetic polymeric materials and an anti-tracking filler system containing at least 20 percent by weight of alumina trihydrate and at least one percent by weight based on the weight of the polymer and filler system of a chemically treated silica filler.
- Penneck discloses tracking resistant insulating materials in U. S. Patent No. 4,189,392, in which the insulating materials contain a polymeric material and an anti-tracking filler and a fluorine substituted compound which is a hydrophobic, non-ionic compound having a fluorine-substituted aliphatic carbon chain linked to a group having an affinity for the polymeric material and/or the anti-tracking filler.
- It is an object of the present invention to provide an organopolysiloxane elastomer having improved adhesion. Another object of the present invention is to provide an organopolysiloxane having an improved contact angle. Still another object of the present invention is to provide an organopolysiloxane having an accelerated cure rate. Still another object of the present invention is to provide an organopolysiloxane elastomer having improved arc resistance. Still another object of the present invention is to provide an organopolysiloxane elastomer which exhibits improved resistance to leakage of electrical current. Still another object of the present invention is to provide a composition which may be applied to the outer surface of insulators to reduce electrical leakage. A further object of the present invention is to provide coated insulators having a longer useful life. A still further object of the present invention is to provide coated insulators which are resistant to arcing.
- The foregoing objects and others which are apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a composition comprising an organopolysiloxane containing reactive groups, an amine crosslinking agent which is capable of crosslinking with the organopolysiloxane and aluminum trihydrate, which has been treated to impart hydrophobic properties thereto. The resultant composition may be applied to the outer surface of electrical insulators and crosslinked in the presence of atmospheric moisture.
- The organopolysiloxanes employed herein are preferably diorganopolysiloxanes having terminal reactive groups and more preferably organopolysiloxanes having terminal hydroxyl groups. These organopolysiloxanes are well known and have been employed heretofore in room temperature vulcanizable (RTV) compositions. The preferred diorganopolysiloxanes, which have terminal hydroxyl groups, may be represented by the formula
- The hydroxyl groups linked to the silicon atoms of the organopolysiloxane can be replaced in part or entirely by other reactive groups such as hydrogen atoms, halogen atoms, alkoxy groups, aryloxy radicals and radicals of the formula R′NH-, where R′ is a cycloalkyl radical of from 5 to 12 carbon atoms.
- The siloxane polymers are essentially linear, hence they are predominately, i.e., at least 90 mole percent are R₂SiO units. However, siloxane units, other than the disiloxane (R₂SiO) units may be present in an amount up to about 5 mol percent and more preferably below about 2 mol percent. Generally, siloxane units such as RSiO3/2 units, R₃SiO½ units and/or SiO4/2 units, where R is the same as above can be present mostly as impurities.
- In the above formula, each R can be a monovalent hydrocarbon radical of up to 18 carbon atoms. Examples of radicals represented by R include alkyl radicals such as the methyl, ethyl, n-propyl, isopropyl, dodecyl and octadecyl radicals; alkenyl radicals such as vinyl, allyl, hexenyl and octadecenyl radicals; cycloalkyl radicals such as the cyclobutyl, cyclopentyl, cyclohexyl and cyclodecyl radicals; cycloalkenyl radicals such as the cyclobutenyl, cyclopentenyl, cyclohexenyl and cyclodecenyl radicals; aryl radicals such as phenyl, xenyl, naphthyl and the phenanthryl radicals; aralkyl radicals such as the benzyl, B-phenylethyl and B- phenylpropyl radicals and alkaryl radicals such as the tolyl, xylyl and ethylphenyl radicals.
- Substituted hydrocarbon radicals represented by R include halogen hydrocarbon radicals such as o-, m- and p-chlorophenyl and bromophenyl radicals, α,α,α-trifluorotolyl, 3,3,3-trifluoropropyl, chloro-, fluoro- and bromoderivatives of the various hydrocarbon radicals set forth above as well as cyanoalkyl radicals such as B-cyanoethyl, cyanopropyl, cyano-n-butyl, cyano-n-propyl and omega-cyanooctadecyl radicals.
- Preferably, the radicals represented by R have less than 8 carbon atoms and more preferably R represents methyl, ethyl, propyl, vinyl, phenyl, and 3,3,3-trifluoropropyl radicals. Of course, as is usually the case, the R radicals on a single silicon atom can be the same or different and various units in the siloxane chain can be the same or different homopolymers, e.g., dimethylsiloxane units, copolymers of, for example, dimethylsiloxane and methylvinylsiloxane units, or phenylmethylsiloxane units and mixtures thereof. The siloxane polymers employed can vary from relatively mobile fluids (viscosity 50 mPa.s at 25°C) to gum-like materials having viscosities in the range of 10⁶ mPa.s at 25°C. This can be seen from the value of n in the general formula above, where n is at least 3 and is preferably at least 50, but can have a value as high as 2,000,000. The preferred siloxane polymers are those having viscosities in the range of from 200 to 200,000 mPa.s at 25°C.
- These siloxanes are known and have been described in, for example, U. S. Patents Nos. 3,294,732; 3,127,363; 3,105,061 and others.
- The room temperature vulcanizable organopolysiloxane compositions are prepared by mixing under anhydrous conditions organopolysiloxanes containing reactive groups, preferably hydroxyl groups, with an amine-substituted silicon compound capable of reacting with the organopolysiloxane reactive groups and having an average of at least two -NR½ groups bonded to a silicon atom per molecule, where R¹ is a monovalent hydrocarbon radical which preferably has up to 18 carbon atoms or hydrogen, and more preferably at least one R¹ is hydrogen.
- Amine-substituted silicon compounds which may be employed as crosslinking agents are aminosilanes of the formula
R²4-zSi(NR½ )z
where R¹ is the same as above and R² is a monovalent radical, preferably a monovalent hydrocarbon radical, having from 1 to 18 carbon atoms, and z has an average value of at least 2 and more preferably from 2 to 4 per molecule and partial hydrolyzates thereof. - The aminosilanes which are employed as crosslinking agents preferably may contain an average of 3 or 4 amino substituents per silicon atom and 0 or 1 alkyl, or aryl, or alkaryl or aralkyl radicals per silicon atom. In general, the trifunctional aminosilanes may be represented by the formula R²Si(NR½ )₃ and the tetra-functional silanes by the formula Si(NR½ )₄, where R¹ and R² are the same as above. Specific examples of monovalent hydrocarbon radicals represented by R¹ are alkyl radicals, such as the methyl, ethyl, propyl or octadecyl radicals, aryl radicals, such as the phenyl or anthracyl or a cycloalkyl radical such as the cyclohexyl radical or an aralkyl radical such as the benzyl or phenylethyl radical or an alkaryl radical such as the tolyl or xylyl radicals. Examples of monovalent hydrocarbon radicals represented by R² are an alkyl, aryl, cycloalkyl, alkaryl or aralkyl radicals. The specific examples recited for the R¹ radicals also apply to the R² radicals, when R¹ is a monovalent hydrocarbon radical. Only one type of aminosilane need be employed; however, mixtures of aminosilanes may also be employed as crosslinking agents.
- Other amino-substituted silicon compounds which may be employed as cross-linking agents are aminosiloxanes having the general formulas
- Divalent saturated hydrocarbon radicals represented by R³ above are methylene, ethylene, propylene, butylene, hexylene, octylene and decylene radicals. Divalent unsaturated hydrocarbon radicals represented by R³ are ethenylene, propenylene, butenylene, hexenylene, octenylene and decenylene radicals. An example of a divalent cyclic hydrocarbon radical is the phenylene radical.
- The aminosilanes and aminosiloxanes and aminosilylalkanes employed as crosslinking agents are described, for example, in U. S. Patents Nos. 3,408,325 to Hittmair et al; 3,464,951 to Hittmair et al; 3,452,964 to Creamer; 3,644,434 to Hittmair et al; and 3,816,164 to Pepe et al, all of which are incorporated herein by reference.
- Other amine-substituted silicon compounds which may be employed as cross-linking agents in the compositions of this invention may be represented by the formula
R
where R² and z are the same as above, R⁴ which may be the same or different represent monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms, and more preferably from 1 to 4 carbon atoms. Preferably, R⁴ is an alkyl radical, such as the methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl and octadecyl radicals. Other radicals represented by R⁴ are aryl radicals such as the phenyl radical, alkaryl radicals such as the tolyl and ethylphenyl radicals and aralkyl radicals such as the benzyl and the B-phenylethyl radicals. -
-
- These crosslinking agents may be prepared, for example, by reacting halosilanes with a sec-butylamine. These secondary butylamine crosslinking agents and their method of preparation are described in U. S. Patent No. 3,923,736 to Nitzsche et al, which is incorporated herein by reference.
- The silicon valences of the amine substituted silicon compounds which are not satisfied by the -NCH(R⁴)₂ groups are preferably satisfied by monovalent hydrocarbon radicals, cyanoalkyl radicals, Si-bonded hydroxyl groups and/or siloxane oxygen atoms.
- The amine-substituted organosilicon compounds are employed in amounts which will provide at least one gram equivalent silicon atom of the amih, substituted organosilicon compound per gram equivalent of reactive groups on the organopolysiloxane. Generally from about 0.2 to 40 parts by weight of amine substituted organosilicon compound is added for each 100 parts by weight of the organopolysiloxane containing reactive groups.
- In addition to the organopolysiloxane polymer and amine-substituted organosilicon compound, the composition also contains aluminum trihydrate, which has been treated to impart hydrophobic properties thereto. Preferably, the aluminum trihydrate has a specific surface area in the range of from about 1 to 20 m²/g and more preferably from about 2 to 15 m²/g. The average particle size ranges from about 2 to 10 µm and more preferably from about 2 to 5 µm. Preferably, about 97 percent of the aluminum trihydrate has a particle size of less than about 10 µm.
- Generally, the aluminum trihydrate is present in an amount of from about 40 to 75 percent by weight and more preferably from about 50 to 70 percent by weight based on the weight of the organopolysiloxane polymer and the aluminum trihydrate.
- Any organosilicon compound capable of imparting hydrophobic properties to inorganic substances may be used to treat the aluminum trihydrate of this invention. Organosilicon compounds which may be employed to treat the aluminum trihydrate are those having the general formula
(R₃Si)aZ or Ra,SiZ′4-a′
wherein R which may be the same or different represents monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals having up to 18 carbon atoms, Z and Z′ represent halogen, hydrogen or a radical of the formula -OH, -OR⁴, NX₂, -NR⁴X, -ONR⁴, or -OOCR⁴ and when a is 2, then Z may also represent -O- or -NX-; R⁴ is a monovalent hydrocarbon radical having up to 18 carbon atoms and more preferably R⁴ is an alkyl radical having from 1 to 4 carbon atoms; X is hydrogen or has the same meaning as R⁴, a is 1 or 2 and a′ is 1, 2 or 3. Other organosilicon compounds which may be employed are octamethycyclotetrasiloxane and/or dimethylpolysiloxanes having from 2 to 12 siloxane units per molecule in which the dimethylpolysiloxanes have an Si-bonded hydroxyl group in each of their terminal units. - The monovalent and halogenated monovalent hydrocarbon radicals represented by R in the organosilicon compounds may be the same as the R radicals linked to the diorganopolysiloxanes. Suitable monovalent hydrocarbon radicals having from 1 to 18 carbon atoms are alkyl radicals, cycloalkyl radicals, alkenyl radicals, aryl radicals, alkaryl radicals, aralkyl radicals and halogenated derivatives thereof.
- Examples of halogen atoms represented by Z and Z′ are chlorine, bromine and iodine, with chlorine being the preferred example, since it is readily available.
- Preferred examples of hydrocarbon radicals represented by R⁴ are the methyl, ethyl, propyl and butyl radicals. Additional examples of hydrocarbon radicals represented by R⁴ are described in the following examples of organosilicon compounds which impart hydrophobic properties to aluminum trihydrate.
- Suitable examples of organosilicon compounds which may be employed to impart hydrophobic properties to aluminum trihydrate are hexamethyldisilazane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylethoxysilane, trimethylaminosilane, trimethylchlorosilane, dimethyldiethoxysilane, trimethylsilylisopropylamine, trimethylsilylethylamine, phenyldimethylsilylpropylamine, vinyldimethylsilylbutylamine, diethylaminoxytrimethylsilane, diethylaminoxyphenyldimethylsilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisilazane, dimethyldichlorosilane, dimethyldimethoxysilane, diphenyldiethoxysilane, vinylmethyldimethoxysilane, and methyltriethoxysilane.
- It is preferred that the organosilicon compound used to treat the aluminum trihydrate be a vinyltrialkoxysilane having 1 to 2 carbon atoms per alkoxy group because they do not release any by-products which may have a detrimental effect on the dispersions of this invention.
- Mixtures of various organosilicon compounds may also be employed in the treatment of aluminum trihydrate to impart hydrophobic properties thereto.
- It is preferred that the amount of organosilicon compounds used in the surface treatment of the aluminum trihydrate be from about 0.1 to 10 percent by weight based on the weight of the aluminum trihydrate.
- The aluminum trihydrate can be reacted with the organosilicon compounds by any conventional technique known in the art for reacting inorganic substances which are solid at room temperature.
- Also, it is possible to react the aluminum trihydrate with hydrophobic imparting organosilicon compounds which evaporate at room temperature at 760mm Hg (abs.), in a sealed container, such as, for example, a polyethylene bag, for a period of time under ambient conditions. In addition, the aluminum trihydrate can be mixed in a mechanical mixing device with a liquid hydrophobic imparting organosilicon compound or in a fluidized bed, and if desired, in the presence of a stream of inert gas.
- The reaction of the aluminum trihydrate with the organosilicon compound can be accelerated by using catalysts such as ammcnia or amines at the rate of from about 0.3 to 3 percent by weight based on the weight of the aluminum trihydrate.
- The compositions of this invention may be prepared by mixing the various ingredients in any order desired; however, the mixture should be prepared in an atmosphere which is substantially free of water.
- In addition to the organopolysiloxane polymer, the amine-substituted organosilicon compound and the treated aluminum trihydrate, the compositions of this invention may also contain additives such as compression-set additives, pigments, soluble dyes, aromatics (essential oils), oxidation inhibitors, heat stabilizers, flame retardants and light stabilizers, plasticizers and softeners such as trimethylsiloxy endblocked dimethylpolysiloxane fluids, reinforcing fillers and non-reinforcing fillers.
- Examples of reinforcing fillers and non-reinforcing fillers are quartz, diatomaceous earth, calcium silicate, zirconium silicate, so-called "molecular sieves", metal oxide powders, such as titania, alumina, iron oxide, zinc oxide and calcium carbonate. Fibrous fillers, for example, asbestos, glass fibers or organic fibers can also be used.
- The fillers can advantageously be treated by known methods to include organosiloxy or alkoxy groups on their surface. Mixtures of different fillers may be added to the compositions of this invention. The amount of filler may vary over a broad range, preferably from 0 to 90 percent by weight, based on the total weight of the organopolysiloxane and filler; however, the amount of filler should not be so great as to degrade the arc resistance or current leakage supression of the elastomeric coating.
- Other additives which may be employed in the compositions of this invention are condensation catalysts such as those disclosed in, for example, U. S. Patents Nos. 2,843,555; 2,127,363; and 3,082,527. Examples of suitable condensation catalysts are metallic salts and organometallic salts of carboxylic acids, such as lead octoate, dibutyltin dilaurate and dibutyltin salts of aliphatic carboxylic acids which are branched in the alpha-position to the carboxyl groups and have from 9 to 11 carbon atoms, amines, such as 3-ethoxypropylamine-1, and silanes which have at least one amine group bonded via carbon to silicon and at least one monovalent hydrocarbon radical or a hydrocarbon radical substituted by an amine group and/or alkoxy group, and bonded via oxygen to silicon in each molecule. Silanes of the latter, which not only act as condensation catalysts but as adhesion promoters for improving the adhesion of the elastomers to the substrates, are N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane or a compound of the formula
CH₃Si[O(CH₂)₂NH₂]₂(CH₂)₃O(CH₂)₂NH₂ . - If condensation catalysts are used, they are generally employed in amounts of from 0.01 to 5 percent by weight and more preferably from about 0.05 to 1 percent by weight, based on the total weight of the composition.
- When adhesion promoters are employed in the compositions, the amount may range from about 0.2 to about 2 percent by weight, based on the weight of the organopolysiloxane and aluminum trihydrate.
- The compositions of this invention are preferably prepared by mixing the treated aluminum trihydrate with the organopolysiloxane containing reactive groups and the mixture deaired. The amine-substituted organosilicon crosslinking agent and catalyst, if used, is then added to the mixture under anhydrous conditions.
- The compositions of this invention may be stored for long periods of time under anhydrous conditions without deletrious effects and then crosslinked by merely exposing them to atmospheric moisture at room temperature.
- The compositions of the present invention are especially useful for coating high voltage apparatus where it is essential that a component be insulated from the sur rounding elements.
- High voltage insulators, preferably ceramic or plastic insulators, may be coated with the compositions of this invention by conventional methods, such as spraying, dipping or brushing. Generally, the compositions are dispersed in a non-reactive solvent for ease of application. Examples of non-reactive solvents which may be employed are hydrocarbon solvents such as toluene, xylene, naphtha and chlorinated hydrocarbon solvents such as chlorothene. Preferred solvent are chlorinated hydrocarbon solvents, especially chlorothene and V.M.&P naphtha. By dispersing the composition in a solvent, the viscosity can be reduced so that it can be applied to the insulator surface by spraying, dipping or brushing.
- The amount of non-reactive solvent is not critical and may range up to about 80 percent by weight, based on the weight of the composition.
- The coatings of this invention may be crosslinked by exposing the coating to atmospheric moisture. Crosslinking may be accelerated by applying heat or by adding water in addition to that contained in the atmosphere or by the addition of carbon dioxide.
- The coating preferably ranges from about 0.2 to about 2 mm in thickness. A coating thickness above about 2 mm may be applied to the insulators, if desired. It has been found that a thicker coating may be more resistant to arcing than thinner coatings, such as those having a thickness of less than about 0.2 mm.
- An advantage of the present invention is that a coated insulator can be manufactured in place. Insulators such as ceramic suspension insulators, strings, ceramic post insulators, composite suspension insulators, filled-resin post insulators and cable terminations can be coated in the field by applying the compositions of this invention on the surfaces of the insulators and thereafter exposing the coated surface to atmospheric moisture to crosslink the same. The resultant coating forms a hydrophobic arc-resistant surface. Also, insulators may be sprayed on line and the line re-energerized while the coating dries and cures in the presence of atmospheric moisture.
- These compositions are useful in a number of applications where it is necessary to resist erosion and/or control current leakage, and are especially useful in electrical components exposed to voltages above 1 kV. The compositions may be used in electrical power transmission and distribution systems, as for example, insulator materials for high voltage components, as insulators for cable terminations, fuse covers, transformer covered and as insulation coatings.
- Surprisingly, it was found that the use of aluminum trihydrate treated with a hydrophobic agent provided an elastomer having an improved contact angle. It has been shown heretofore that there is a close correlation between the hydrophobic nature of the surface as measured by contact angle with water and the electrical performance of the elastomer.
- In the following examples all parts are by weight unless otherwise specified.
- To a mixer containing 100 parts of a hydroxyl-terminated dimethylpolysiloxane having a viscosity of 20,000 mPa.s at 25°C are added 150 parts of treated aluminum trihydrate (available from Solem Industries, Inc. as SP-632) and mixed for about 20 minutes under a nitrogen atmosphere. Then about 82 parts of chlorothene are added to the mixture and mixed for about 10 minutes to form a dispersion. About 10 parts of methyltris-(cyclohexylamino)silane and 0.8 parts of gamma-aminopropyltrimethoxysilane are then added to the dispersion and mixed for about 20 minutes under a nitrogen atmosphere. The resultant dispersion is molded to form test specimens and exposed to atmospheric moisture for 7 days. The skin-over time is 6 minutes and the tack-free time is 11 minutes. The physical properties are determined after curing for 7 days in atmospheric moisture.
Physical Properties Durometer, Shore A 55 Tensile strength 2,069 MPa (300 psi) Elongation percent 125 Tear strength 5260 N/m ( 30 ppi) - The arc resistance of a cured sample is determined in accordance with ASTMD-495-73.
- Arc resistance to failure > 420 seconds
- The contact angle is measured by the sessile drop technique in which drops of water about 2 mm in diameter are applied from a syringe to the surface of the sample after it has cured for 7 days. The contact angle is measured about 30 seconds after applying the water using a telescope fitted with a goniometer eyepiece.
- Contact angle of the cured sample is 103°.
- The procedure of Example 1 is repeated, except that 150 parts of an untreated aluminum trihydrate (available from Solem Industries, Inc. as SB-632) is substituted for the treated aluminum trihydrate. The resultant mixture is formed into test specimens and exposed to atmospheric moisture. The skin-over time is 11 minutes and the tack-free time is 18 minutes. After curing for 7 days in atmospheric moisture, the physical properties are determined.
Physical Properties Durometer, Shore A 50 Tensile strength 1,655 MPa (240 psi) Elongation, percent 150 Tear strength 5260 N/m ( 30 ppi) - The contact angle, which is measured in accordance with the procedure described in Example 1, is 90°.
- The procedure of Example 1 is repeated, except that 67 parts of treated aluminum trihydrate is substituted for 150 parts of treated aluminum trihydrate. The resultant composition exhibited good arc resistance.
- The procedure of Example 1 is repeated, except that 300 parts of treated aluminum trihydrate is substituted for 150 parts of treated aluminum trihydrate. The arc resistance of the resultant composition before failure is greater than 420 seconds.
- The solvent dispersion prepared in accordance with the procedure of Example 1 is applied to the surface of a ceramic insulator as a uniform coating about 1 mm in thickness and cured by exposure to atmospheric moisture. The resultant coating provides a hydrophobic and arc resistant surface which shows excellent adhesion to the insulator surface.
- The procedure of Example 1 is repeated, except that 10 parts of each of the following crosslinking agents are substituted for 10 parts of methyltris(cyclohexylamino)silane in the above composition: Methyltris(ethylamino)silane, methyltris(phenylamino)silane, methyltris(n-heptylamino)silane, phenyltris(3,5,5-trimethylcyclohexylamino)silane, methyltris(sec-butylamino)silane, tetrakis(n-butylamino)silane, phenyltris(dimethylamino)silane, hexyltris(n-butylamino)silane, ethyltris(methylhexylamino)silane, vinyltris(phenylamino)silane and a mixture containing 30 percent by weight dimethylbis(cyclohexylamino)silane and 70 percent by weight of vinyltris(n-propylamino)silane, based on the weight of the mixture of crosslinking agents. The resultant compositions cured at room temperature to form elastomers having excellent arc resistant properties.
Claims (10)
R
where R¹ is selected from the group consisting of a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and hydrogen, R² is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and z has an average value of from 2 to 4 and partial hydrolyzates thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/118,125 US4822830A (en) | 1987-11-09 | 1987-11-09 | Organopolysiloxane elastomers having improved electrical properties and insulators coated therewith |
US118125 | 1987-11-09 |
Publications (3)
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EP0316696A2 true EP0316696A2 (en) | 1989-05-24 |
EP0316696A3 EP0316696A3 (en) | 1990-10-31 |
EP0316696B1 EP0316696B1 (en) | 1995-07-19 |
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US (1) | US4822830A (en) |
EP (1) | EP0316696B1 (en) |
JP (1) | JPH01123861A (en) |
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AU (1) | AU604438B2 (en) |
CA (1) | CA1306824C (en) |
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EP0787772A3 (en) * | 1996-01-30 | 1998-01-07 | Dow Corning Toray Silicone Company Ltd. | Silicone rubber composition |
EP0808868B1 (en) * | 1996-05-24 | 2000-04-12 | Dow Corning Toray Silicone Company Ltd. | Silicone rubber composition for application as electrical insulation |
EP1113048A3 (en) * | 1999-12-27 | 2002-01-30 | General Electric Company | Hydrophobicity imparting particulate |
US6670418B2 (en) | 1996-11-06 | 2003-12-30 | Wacker-Chemie Gmbh | Crosslinkable organopolysiloxane compositions |
EP1853393A4 (en) * | 2005-02-25 | 2011-01-05 | Csl Silicones Inc | Title: method and apparatus for automated coating of electrical insulators with a silicone composition |
CN109476804A (en) * | 2016-07-21 | 2019-03-15 | Sika技术股份公司 | Flame retardant adhesives and sealants with improved mechanical properties |
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US5326804A (en) * | 1991-02-01 | 1994-07-05 | Balwantrai Mistry | Organopolysiloxane rubber composition for coating high voltage electrical insulators having improved electrical properties |
US5641827A (en) * | 1996-03-20 | 1997-06-24 | Raychem Corporation | Tracking and erosion resistant composition |
US6255738B1 (en) | 1996-09-30 | 2001-07-03 | Tessera, Inc. | Encapsulant for microelectronic devices |
US6103804A (en) * | 1998-10-07 | 2000-08-15 | Wacker Silicones Corporation | Process for the sealing components exposed to aggressive functional fluids and RTV silicone compositions suitable for use therein |
US6156285A (en) * | 1998-11-12 | 2000-12-05 | Dow Corning Corporation | Method for densifying particulate silica |
US6153261A (en) * | 1999-05-28 | 2000-11-28 | Applied Materials, Inc. | Dielectric film deposition employing a bistertiarybutylaminesilane precursor |
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US20030113461A1 (en) * | 2001-12-14 | 2003-06-19 | Farooq Ahmed | Coated composite high voltage electrical insulator |
JP4440517B2 (en) * | 2002-05-07 | 2010-03-24 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition and parts using the composition as an adhesive |
US7013977B2 (en) * | 2003-06-11 | 2006-03-21 | Halliburton Energy Services, Inc. | Sealed connectors for automatic gun handling |
JP5855552B2 (en) * | 2012-10-15 | 2016-02-09 | 信越化学工業株式会社 | Method for producing polyorganosiloxane |
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EP0787772A3 (en) * | 1996-01-30 | 1998-01-07 | Dow Corning Toray Silicone Company Ltd. | Silicone rubber composition |
US5824729A (en) * | 1996-01-30 | 1998-10-20 | Dow Corning Toray Silicone Co., Ltd. | Silicone rubber composition |
EP0808868B1 (en) * | 1996-05-24 | 2000-04-12 | Dow Corning Toray Silicone Company Ltd. | Silicone rubber composition for application as electrical insulation |
US6670418B2 (en) | 1996-11-06 | 2003-12-30 | Wacker-Chemie Gmbh | Crosslinkable organopolysiloxane compositions |
EP1113048A3 (en) * | 1999-12-27 | 2002-01-30 | General Electric Company | Hydrophobicity imparting particulate |
US6582825B2 (en) | 1999-12-27 | 2003-06-24 | General Electric Company | Hydrophobicity imparting particulate |
EP1853393A4 (en) * | 2005-02-25 | 2011-01-05 | Csl Silicones Inc | Title: method and apparatus for automated coating of electrical insulators with a silicone composition |
CN109476804A (en) * | 2016-07-21 | 2019-03-15 | Sika技术股份公司 | Flame retardant adhesives and sealants with improved mechanical properties |
Also Published As
Publication number | Publication date |
---|---|
DE3854185D1 (en) | 1995-08-24 |
AU604438B2 (en) | 1990-12-13 |
ATE125281T1 (en) | 1995-08-15 |
AU1914888A (en) | 1989-05-25 |
EP0316696A3 (en) | 1990-10-31 |
CA1306824C (en) | 1992-08-25 |
EP0316696B1 (en) | 1995-07-19 |
DE3854185T2 (en) | 1995-12-07 |
JPH01123861A (en) | 1989-05-16 |
US4822830A (en) | 1989-04-18 |
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